CA1229092A - Compounds containing quaternary ammonium and methylenephosphonic acid groups - Google Patents
Compounds containing quaternary ammonium and methylenephosphonic acid groupsInfo
- Publication number
- CA1229092A CA1229092A CA000456808A CA456808A CA1229092A CA 1229092 A CA1229092 A CA 1229092A CA 000456808 A CA000456808 A CA 000456808A CA 456808 A CA456808 A CA 456808A CA 1229092 A CA1229092 A CA 1229092A
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- Prior art keywords
- compound
- acid
- carbon atoms
- iii
- salts
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 21
- 239000002253 acid Substances 0.000 title claims description 22
- 125000001453 quaternary ammonium group Chemical group 0.000 title 1
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 3
- -1 trialkylammonium halide Chemical class 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 159000000000 sodium salts Chemical group 0.000 claims 1
- 229920000768 polyamine Polymers 0.000 abstract description 7
- VFKZECOCJCGZQK-UHFFFAOYSA-M 3-hydroxypropyl(trimethyl)azanium;chloride Chemical group [Cl-].C[N+](C)(C)CCCO VFKZECOCJCGZQK-UHFFFAOYSA-M 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 3
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 150000001412 amines Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- 229940116254 phosphonic acid Drugs 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000005764 inhibitory process Effects 0.000 description 7
- 229960000443 hydrochloric acid Drugs 0.000 description 6
- 235000011167 hydrochloric acid Nutrition 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 4
- 229960004279 formaldehyde Drugs 0.000 description 4
- 235000019256 formaldehyde Nutrition 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004148 curcumin Substances 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RUUHDEGJEGHQKL-UHFFFAOYSA-M 2-hydroxypropyl(trimethyl)azanium;chloride Chemical group [Cl-].CC(O)C[N+](C)(C)C RUUHDEGJEGHQKL-UHFFFAOYSA-M 0.000 description 1
- VLRGXXKFHVJQOL-UHFFFAOYSA-N 3-chloropentane-2,4-dione Chemical compound CC(=O)C(Cl)C(C)=O VLRGXXKFHVJQOL-UHFFFAOYSA-N 0.000 description 1
- FTQHZWWAJOEHML-UHFFFAOYSA-M 3-hydroxypropyl(tripropyl)azanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCCO FTQHZWWAJOEHML-UHFFFAOYSA-M 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- DOWCFWXDUFIZSX-UHFFFAOYSA-M [Br-].OC(C)[N+](CC)(CC)CCC Chemical compound [Br-].OC(C)[N+](CC)(CC)CCC DOWCFWXDUFIZSX-UHFFFAOYSA-M 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- SXYCCJAPZKHOLS-UHFFFAOYSA-N chembl2008674 Chemical compound [O-][N+](=O)C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3O)=C(O)C=C(S(O)(=O)=O)C2=C1 SXYCCJAPZKHOLS-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical group CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 150000003945 chlorohydrins Chemical class 0.000 description 1
- 229940042400 direct acting antivirals phosphonic acid derivative Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical class C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical class [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3817—Acids containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Detergent Compositions (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Compounds having improved properties of inhibiting the precipitation of metal ions when used in threshold amounts have been made which are derivatives of ammonia or di- or polyamines in which the amine hydrogens have been substituted with both methylene-phosphonic acid groups or their salts and hydroxypropyl quaternaryammonium halide groups. Thus, ammonia can have two hydrogens replaced with methylenephosphonic groups while the third is replaced with a hydroxypropyl-trimethylammonium chloride group; and three hydrogens of ethylenediamine can be replaced with methylenephos-phonic groups, the fourth being replaced with a hydroxy-propyltrimethylammonium chloride group.
Compounds having improved properties of inhibiting the precipitation of metal ions when used in threshold amounts have been made which are derivatives of ammonia or di- or polyamines in which the amine hydrogens have been substituted with both methylene-phosphonic acid groups or their salts and hydroxypropyl quaternaryammonium halide groups. Thus, ammonia can have two hydrogens replaced with methylenephosphonic groups while the third is replaced with a hydroxypropyl-trimethylammonium chloride group; and three hydrogens of ethylenediamine can be replaced with methylenephos-phonic groups, the fourth being replaced with a hydroxy-propyltrimethylammonium chloride group.
Description
~ 9 ~ ~
NEW COMPOUNDS CO~TAINING QUATERNARY Ah~lONIUM
AND METHYLENEPHOSPHONIC ACID GROUPS
The use of methylenephosphonic acid substituted alkylene polyamines ~or metal ion control at less than stoichiometric amounts was suggested in a patent to Bersworth ~U.S. 2,609,390) in 1952. Later a wa-ter dispersible polymeric amine chelating agent which included alkylene phosphonate derivatives was indicated as having "threshold" effects in scale inhibition applications (see U.S. 3,331,773), this term being used to describe the use of the agent in less than stoichio-metric amounts. The diamine and polyamine methylene-phosphonate derivatives are taught and claimed in U.S.
patents 3,336,221 and 3,434,969, respectively. Some of the products disclosed in these two patents are available commercially and are recommended as scale inhibitors when applied in threshold amounts.
Some other patents disclose heterocyclic nitrogen containing compounds which are useful ~s chelating agents and may be employed in ~hreshold amounts are U.S. 3,674,804; 3,720,498; 3,743,603;
~0 3,859,~11; and 3,~54,761.
30,724-F -1-Methylenephosphonates of polyalkylene poly-amines, disclosed in U.S. patent 4,051,110, are made by reacting di- or polyamines with a chain extending agent such as a dihalide or an epoxyhalide, e.g. ethylene dichloride or epichlorohydrin and thereafter, with phosphorous acid and formaldehyde. Thus, for example, triethylenetetramine is reacted with epichlorohydrin in an approximately one to one mole ratio; thereafter the product is reacted with phosphorous acid, and formalde-hyde in the presence of hydrochloric acid. The resultingmethylenephosphonated polyamine is useful in small amounts as a scale inhibitor, being employed at con-centrations of 20-50 ppm.
Certain phosphonic acid derivatives of the aliphatic acids can be prepared by reacting phosphorous acid with acid anhydrides or acid chlorides, e.g. the anhydrides or chlorides of acetic, propionic and valeric acids. The compounds prepared have the formula O R O
~HO)2-P-C-P-(OH)2 OH
wherein R is a lower alkyl radical having 1 to 5 carbon atoms. The method of making and using these products is described in U.S. Patent 3,214,454. The use of threshold amounts to prevent calcium precipitation is disclosed and claimed therein.
Compounds such as the reaction product of a halohydrin, e.g. epichlorohydrin, with an amine, e.g.
trimethylamine, give quaternary ammonlum chlorohydrin adducts, which have biological activity. The chlorine of the chlorohydrin moiety can, of course, be reacted 30,724-F -2-~2~9~
wlth another amine to give a hydroxyalkyl quaternary ammonium compound and adduct of the amine.
It has now been discovered that such a function-ality when attached to a diamine or polyamine which also contains a me~hylenephosphonic acid group will give a compound having improved threshold activity, i.e. inhibits precipitation of metal ions from solution at less than stoichiometric amounts.
Briefly, the invention comprises compounds having improved properties of inhibiting the precipi-tation of metal ions when used in threshold amounts have been made which are derivatives of a~nonia or di-or polyamines in which the amine hydrogens have been substituted with both methylenephosphonic acid groups or their salts and 2-hydroxy-3(trialkylammonium halide) propyl groups. These compounds have the formula B C
A-N-~CH2CH2N~n-D
wherein sub~tituents A, B, C and D are each independ-ently ~elected from hydrogen; methylenephosphonic acid or salts thereof; 2-hydroxy-3(trialkylammonium halide~ propyl wherein ea~h alkyl moiety contains from 1 to 5 carbon atoms; a moiety of the formula O
~R-C-OH
wherein R ~s an unsubstituted or inertly sub-stituted alkyl group having 1 to 6, preferably 1 to 3, more preferably 1 carbon atoms, or salts thereof, n is O to 15; and wherein said substituents 30~7~4 F -3-z~g;~
include at least one methylenephosphonic acid group, or salt thereof, and at least one 2-hydroxy-3(tri-alkyla~nonium halide) propyl group.
Reactants used to prepare the products of the invention are ammonia, alkyleneamines, polymeric amines and polyethyleneimines of different molecular weights, such as those from Cordova Chemical Company. Various metal and alkali metal salts, a~nonium and amine salts and partial sal-ts of the methylenephosphonic acids and mixtures thereof can be utilized to make the quaternized derivatives of the invention. It should be noted, however, that the quaternization of the amine preferably should precede the phosphonomethylation and the making of any of the methylenephosphonic acid salts.
Almost any amine that contains reactive aminohydrogens can be utilized to prepare the products.
Thus for example, polyglycolamines, amidoamines, oxy-alkylated amines, carboxymethylated amines, methylene-sulfonated and hydroxypropylsulfonated amines, nitrogen-heterocyclics, and the like can be employed as a reactant.
The pre~erred products are those that have had the aminohydrogens fully replaced although some aminohydro-gens can be left unreacted.
The Pollowing examples are representative of making the com~ounds of the invention and of making the completely phosphona~ed compounds for comparison.
Eth~lenedlamine ~EDA~ (lS ~, Q.25 mole) and 94 g (0.25 mole~ of a 50% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride were added to a 30,7~4~ 4-500 ml round-bottom reaction flask equipped with a water-cooled reflux condenser, mechanical stirrer, thermometer with a temperature controller, and an addition funnel. The reaction mixture was heated to 90C and digested for about one hour and cooled.
Approximately 60 g of concentrated hydrochloric acid solution and 67.5 g (0.82 mole) of phosphorous acid were added to the reaction flask and heated to reflux and maintained for one hour. Aqueous 37% formaldehyde 10 solution (67.4 g, 0.83 mole) was weighed into the addition funnel and added over a two-hour period. The reaction mixture was heated at reflux for an additional three hours and then cooled. The product was the derivative o~ EDA in which one hydrogen had been replaced with 2-hydroxypropyltrimethylammonium chloride groups and the remaining hydrogens with methylenephosphonic acid groups.
EXAMP_E 2 (Comparative) Ethyleneamine E-100* (12.5 g) and 12.5 g of deionized water were added to a 500-ml round-bottom reaction flask equipped as described in Example 1.
Approximately 110 g of concentrated hydrochloric acid solution and 31.1 g (0.38 mole) of phosphorous acid were added to the reaction flask and heated to reflux and malntained for one hour. Aqueous 37% formaldehyde solution (26.8 g, 0.33 mole) was weighed into the addition ~unnel and added over a one-hour period. The - reaction mixture was heated at reflux for an additional three hours and then cooled. The product was the derivative of E-100 in which all amine hydrogens had been replaced with methylenephosphonic acid groups.
~. . .
30,724-F -S-6- ~2~
Ethyleneamine E-lO0* (12.5 g) and 12.5 g of deionized water were added to a 500-ml round-bottom reaction flask as in Example 2 and heated to 90C. A
50% aqueous solution of 3-chloro-2~hydroxypropyl-trimethylammonium chloride (12.0, O.032 mole) was weighed into the addition funnel and added over about a 10-minute period. The reaction mixture was heated for an additional hour at 90C and cooled. Approximat~ly 110 g of concentrated hydrochloric acid solution and 28.5 g (0.35 mole) of phosphorous acid were added to the reaction flask and heated to reflux and maintained for one hour. Aqueous 37% formaldehyde solution (24.5, 0.30 mole) was weighed into the addition funnel and added over a one-hour period. The reaction mixture was heated at reflux for an additional three hours and then cooled. The product was the E-100 derivative in which ~10% of the amine hydrogens had been replaced with hydroxypropyltrimethylammonium chloride groupsl the ~0 remainder being replaced with methylenephosphonic acid groups.
EXAMPLE 4 (Comparative) An aqueous polymeric polyalkylenepolyamine (PAPA) solution (66.4 g of 36,~), prepared from ethylene-amine E-100 and ethylene dichloride, was aclded to a 500-ml round-bottom reaction flask equipped as in ~Ethyleneamine E-100 is a product of The Dow Chemical Company and is described as a mixture of pentaethylene-hexamine plus heavier ethyleneamines wlth an average molecular weight of ~S0-300.
30,7~4-F _~_ ~2~
Example l. Approximately 40 g of concentrated hydro-chloric acid solution and 49.3 g (0.60 mole) of phos-phorous acid were added to the reaction flask and heated to reflux and rnaintained for one hour. Aqueous 37% formaldehyde solution (51.1 g, 0.63 mole) was weighed into the addition funnel and added over a one-hour period. The reaction mixture was heated at re~lux for an additional one and one-half hours and cooled. The product was the PAPA in which all amine hydrogens had been substituted with methylenephosphonic acid groups.
The polymeric polyalkylenepolyamine used in Example 4 was modified by reacting ten mole percent of the available aminohydrogens with 3-chloro-2-hydroxy-propyltrimethylammonium chloride in a similar manner as described in Example 3. The resultant reaction product was then phosphonomethylated with phosphorous acid and formaldehyde in the presence of hydrochloric acid. The product was the PAPA in which ~10% of the amine hydrogens had been replaced with hydroxypropyltrimethylammonium chloride groups, the remainder being replaced with methylenephosphonic acid groups.
The products of ~,xamples 1-5 were evaluated according to the ~ollowin~ scale inhibition test with respect to calcium carbonate: Several 50 ml samples of a 0.02M CaCl2 solution are placed in 4-ounce bottles.
To these solutions is added the candidate inhibitor in various concentrations. Samples (50 ml each) of a 0.04M
sodium bicarbonate/0.96M sodium chloride solution are then added with stirring. A total hardness determination is made on the mixture by adding excess standard EDTA
30,724-F -7-3~
to a sample and back titrating with standard Mg++
solution in the presence of Eriochrome Black T indicator.
The samples are placed in an 80C oven and 10-ml samples taken periodically from each bottle, filtered through a filter having pore diameters of 4-5.5 ~m, and the total hardness of the filtrates determined by titration.
blank with no inhibitor is run in an iden~ical manner.
The relative inhibition effects are shown by determining the amount o~ hardness (as soluble calcium) before and after heating for a 24-hour period. The amount of soluble calcium as a percent of that originally present is indicated as percent inhibition.
Results of these tests are shown in Table I
and compared with the phosphonated, but unquaternized amine. All products and comparative runs were made using a conc~ntration of 10 ppm based on active acid.
TABLE I
Additive % Inhibition .
EDA(CH2P03H2)4 (comparative)* 41.8 20 Product Ex. 1 41.8 . _ _ ............... . .. _ .. _ _ Product Ex. 2 (comparative) 43.4 Product Ex. 3 49 9 .... _ . . _ ~ . _ _ . _ ...
25 Product Ex. 4 ~comparative) 35.0 Product Ex. 5 38.1 . . ~
Blank (no additive) (comparative) 12**
*This phosphonate is a commercially available compound sold for the purpose of scale inhibition.
**This indicates that 88% of the calcium had precipitated in the blank.
30,724-F -8-~22~0~
In the above tests it can readily be seen that the methylenephosphonic acid derivatives which contain at least one quaternary group are at least as good or better than the compounds containing only the methylenephosphonic group, including the derivative of EDA indicated as a commercially available scale inhibi-tion compound. It should be understood that such compounds which contain only the quaternary groups do not exhibit any threshold effect, and that the methylene-phosphonic acid group or its salt must be present forthe effect to be obtained.
While the examples all show the use of the chloride form of the quaternary group, other halides, e.g. Br or I , can be emploYed as the quaternized derivative. Thus, the quaternary salt could be hydroxy-propyltriethylammonium bromide, hydroxypropyltripropyl ammoniumiodide and the like.
30,724-F -~-
NEW COMPOUNDS CO~TAINING QUATERNARY Ah~lONIUM
AND METHYLENEPHOSPHONIC ACID GROUPS
The use of methylenephosphonic acid substituted alkylene polyamines ~or metal ion control at less than stoichiometric amounts was suggested in a patent to Bersworth ~U.S. 2,609,390) in 1952. Later a wa-ter dispersible polymeric amine chelating agent which included alkylene phosphonate derivatives was indicated as having "threshold" effects in scale inhibition applications (see U.S. 3,331,773), this term being used to describe the use of the agent in less than stoichio-metric amounts. The diamine and polyamine methylene-phosphonate derivatives are taught and claimed in U.S.
patents 3,336,221 and 3,434,969, respectively. Some of the products disclosed in these two patents are available commercially and are recommended as scale inhibitors when applied in threshold amounts.
Some other patents disclose heterocyclic nitrogen containing compounds which are useful ~s chelating agents and may be employed in ~hreshold amounts are U.S. 3,674,804; 3,720,498; 3,743,603;
~0 3,859,~11; and 3,~54,761.
30,724-F -1-Methylenephosphonates of polyalkylene poly-amines, disclosed in U.S. patent 4,051,110, are made by reacting di- or polyamines with a chain extending agent such as a dihalide or an epoxyhalide, e.g. ethylene dichloride or epichlorohydrin and thereafter, with phosphorous acid and formaldehyde. Thus, for example, triethylenetetramine is reacted with epichlorohydrin in an approximately one to one mole ratio; thereafter the product is reacted with phosphorous acid, and formalde-hyde in the presence of hydrochloric acid. The resultingmethylenephosphonated polyamine is useful in small amounts as a scale inhibitor, being employed at con-centrations of 20-50 ppm.
Certain phosphonic acid derivatives of the aliphatic acids can be prepared by reacting phosphorous acid with acid anhydrides or acid chlorides, e.g. the anhydrides or chlorides of acetic, propionic and valeric acids. The compounds prepared have the formula O R O
~HO)2-P-C-P-(OH)2 OH
wherein R is a lower alkyl radical having 1 to 5 carbon atoms. The method of making and using these products is described in U.S. Patent 3,214,454. The use of threshold amounts to prevent calcium precipitation is disclosed and claimed therein.
Compounds such as the reaction product of a halohydrin, e.g. epichlorohydrin, with an amine, e.g.
trimethylamine, give quaternary ammonlum chlorohydrin adducts, which have biological activity. The chlorine of the chlorohydrin moiety can, of course, be reacted 30,724-F -2-~2~9~
wlth another amine to give a hydroxyalkyl quaternary ammonium compound and adduct of the amine.
It has now been discovered that such a function-ality when attached to a diamine or polyamine which also contains a me~hylenephosphonic acid group will give a compound having improved threshold activity, i.e. inhibits precipitation of metal ions from solution at less than stoichiometric amounts.
Briefly, the invention comprises compounds having improved properties of inhibiting the precipi-tation of metal ions when used in threshold amounts have been made which are derivatives of a~nonia or di-or polyamines in which the amine hydrogens have been substituted with both methylenephosphonic acid groups or their salts and 2-hydroxy-3(trialkylammonium halide) propyl groups. These compounds have the formula B C
A-N-~CH2CH2N~n-D
wherein sub~tituents A, B, C and D are each independ-ently ~elected from hydrogen; methylenephosphonic acid or salts thereof; 2-hydroxy-3(trialkylammonium halide~ propyl wherein ea~h alkyl moiety contains from 1 to 5 carbon atoms; a moiety of the formula O
~R-C-OH
wherein R ~s an unsubstituted or inertly sub-stituted alkyl group having 1 to 6, preferably 1 to 3, more preferably 1 carbon atoms, or salts thereof, n is O to 15; and wherein said substituents 30~7~4 F -3-z~g;~
include at least one methylenephosphonic acid group, or salt thereof, and at least one 2-hydroxy-3(tri-alkyla~nonium halide) propyl group.
Reactants used to prepare the products of the invention are ammonia, alkyleneamines, polymeric amines and polyethyleneimines of different molecular weights, such as those from Cordova Chemical Company. Various metal and alkali metal salts, a~nonium and amine salts and partial sal-ts of the methylenephosphonic acids and mixtures thereof can be utilized to make the quaternized derivatives of the invention. It should be noted, however, that the quaternization of the amine preferably should precede the phosphonomethylation and the making of any of the methylenephosphonic acid salts.
Almost any amine that contains reactive aminohydrogens can be utilized to prepare the products.
Thus for example, polyglycolamines, amidoamines, oxy-alkylated amines, carboxymethylated amines, methylene-sulfonated and hydroxypropylsulfonated amines, nitrogen-heterocyclics, and the like can be employed as a reactant.
The pre~erred products are those that have had the aminohydrogens fully replaced although some aminohydro-gens can be left unreacted.
The Pollowing examples are representative of making the com~ounds of the invention and of making the completely phosphona~ed compounds for comparison.
Eth~lenedlamine ~EDA~ (lS ~, Q.25 mole) and 94 g (0.25 mole~ of a 50% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride were added to a 30,7~4~ 4-500 ml round-bottom reaction flask equipped with a water-cooled reflux condenser, mechanical stirrer, thermometer with a temperature controller, and an addition funnel. The reaction mixture was heated to 90C and digested for about one hour and cooled.
Approximately 60 g of concentrated hydrochloric acid solution and 67.5 g (0.82 mole) of phosphorous acid were added to the reaction flask and heated to reflux and maintained for one hour. Aqueous 37% formaldehyde 10 solution (67.4 g, 0.83 mole) was weighed into the addition funnel and added over a two-hour period. The reaction mixture was heated at reflux for an additional three hours and then cooled. The product was the derivative o~ EDA in which one hydrogen had been replaced with 2-hydroxypropyltrimethylammonium chloride groups and the remaining hydrogens with methylenephosphonic acid groups.
EXAMP_E 2 (Comparative) Ethyleneamine E-100* (12.5 g) and 12.5 g of deionized water were added to a 500-ml round-bottom reaction flask equipped as described in Example 1.
Approximately 110 g of concentrated hydrochloric acid solution and 31.1 g (0.38 mole) of phosphorous acid were added to the reaction flask and heated to reflux and malntained for one hour. Aqueous 37% formaldehyde solution (26.8 g, 0.33 mole) was weighed into the addition ~unnel and added over a one-hour period. The - reaction mixture was heated at reflux for an additional three hours and then cooled. The product was the derivative of E-100 in which all amine hydrogens had been replaced with methylenephosphonic acid groups.
~. . .
30,724-F -S-6- ~2~
Ethyleneamine E-lO0* (12.5 g) and 12.5 g of deionized water were added to a 500-ml round-bottom reaction flask as in Example 2 and heated to 90C. A
50% aqueous solution of 3-chloro-2~hydroxypropyl-trimethylammonium chloride (12.0, O.032 mole) was weighed into the addition funnel and added over about a 10-minute period. The reaction mixture was heated for an additional hour at 90C and cooled. Approximat~ly 110 g of concentrated hydrochloric acid solution and 28.5 g (0.35 mole) of phosphorous acid were added to the reaction flask and heated to reflux and maintained for one hour. Aqueous 37% formaldehyde solution (24.5, 0.30 mole) was weighed into the addition funnel and added over a one-hour period. The reaction mixture was heated at reflux for an additional three hours and then cooled. The product was the E-100 derivative in which ~10% of the amine hydrogens had been replaced with hydroxypropyltrimethylammonium chloride groupsl the ~0 remainder being replaced with methylenephosphonic acid groups.
EXAMPLE 4 (Comparative) An aqueous polymeric polyalkylenepolyamine (PAPA) solution (66.4 g of 36,~), prepared from ethylene-amine E-100 and ethylene dichloride, was aclded to a 500-ml round-bottom reaction flask equipped as in ~Ethyleneamine E-100 is a product of The Dow Chemical Company and is described as a mixture of pentaethylene-hexamine plus heavier ethyleneamines wlth an average molecular weight of ~S0-300.
30,7~4-F _~_ ~2~
Example l. Approximately 40 g of concentrated hydro-chloric acid solution and 49.3 g (0.60 mole) of phos-phorous acid were added to the reaction flask and heated to reflux and rnaintained for one hour. Aqueous 37% formaldehyde solution (51.1 g, 0.63 mole) was weighed into the addition funnel and added over a one-hour period. The reaction mixture was heated at re~lux for an additional one and one-half hours and cooled. The product was the PAPA in which all amine hydrogens had been substituted with methylenephosphonic acid groups.
The polymeric polyalkylenepolyamine used in Example 4 was modified by reacting ten mole percent of the available aminohydrogens with 3-chloro-2-hydroxy-propyltrimethylammonium chloride in a similar manner as described in Example 3. The resultant reaction product was then phosphonomethylated with phosphorous acid and formaldehyde in the presence of hydrochloric acid. The product was the PAPA in which ~10% of the amine hydrogens had been replaced with hydroxypropyltrimethylammonium chloride groups, the remainder being replaced with methylenephosphonic acid groups.
The products of ~,xamples 1-5 were evaluated according to the ~ollowin~ scale inhibition test with respect to calcium carbonate: Several 50 ml samples of a 0.02M CaCl2 solution are placed in 4-ounce bottles.
To these solutions is added the candidate inhibitor in various concentrations. Samples (50 ml each) of a 0.04M
sodium bicarbonate/0.96M sodium chloride solution are then added with stirring. A total hardness determination is made on the mixture by adding excess standard EDTA
30,724-F -7-3~
to a sample and back titrating with standard Mg++
solution in the presence of Eriochrome Black T indicator.
The samples are placed in an 80C oven and 10-ml samples taken periodically from each bottle, filtered through a filter having pore diameters of 4-5.5 ~m, and the total hardness of the filtrates determined by titration.
blank with no inhibitor is run in an iden~ical manner.
The relative inhibition effects are shown by determining the amount o~ hardness (as soluble calcium) before and after heating for a 24-hour period. The amount of soluble calcium as a percent of that originally present is indicated as percent inhibition.
Results of these tests are shown in Table I
and compared with the phosphonated, but unquaternized amine. All products and comparative runs were made using a conc~ntration of 10 ppm based on active acid.
TABLE I
Additive % Inhibition .
EDA(CH2P03H2)4 (comparative)* 41.8 20 Product Ex. 1 41.8 . _ _ ............... . .. _ .. _ _ Product Ex. 2 (comparative) 43.4 Product Ex. 3 49 9 .... _ . . _ ~ . _ _ . _ ...
25 Product Ex. 4 ~comparative) 35.0 Product Ex. 5 38.1 . . ~
Blank (no additive) (comparative) 12**
*This phosphonate is a commercially available compound sold for the purpose of scale inhibition.
**This indicates that 88% of the calcium had precipitated in the blank.
30,724-F -8-~22~0~
In the above tests it can readily be seen that the methylenephosphonic acid derivatives which contain at least one quaternary group are at least as good or better than the compounds containing only the methylenephosphonic group, including the derivative of EDA indicated as a commercially available scale inhibi-tion compound. It should be understood that such compounds which contain only the quaternary groups do not exhibit any threshold effect, and that the methylene-phosphonic acid group or its salt must be present forthe effect to be obtained.
While the examples all show the use of the chloride form of the quaternary group, other halides, e.g. Br or I , can be emploYed as the quaternized derivative. Thus, the quaternary salt could be hydroxy-propyltriethylammonium bromide, hydroxypropyltripropyl ammoniumiodide and the like.
30,724-F -~-
Claims (11)
1. Compounds having the formula wherein (a) n is 0 to 15;
(b) A, B, C, and D are each independently selected from (i) hydrogen;
(ii) methylenephosphonic acid and salts thereof;
(iii) 2-hydroxy-3(trialkylammonium halide) propyl moieties wherein each alkyl moiety has from 1 to 5 carbon atoms; and (iv) a moiety of the formula wherein R is an unsubstituted or inertly substituted alkyl group having 1 to 6 carbon atoms, or salts thereof;
such that at least one of A, B, C, and D is (ii) and at least one is (iii).
(b) A, B, C, and D are each independently selected from (i) hydrogen;
(ii) methylenephosphonic acid and salts thereof;
(iii) 2-hydroxy-3(trialkylammonium halide) propyl moieties wherein each alkyl moiety has from 1 to 5 carbon atoms; and (iv) a moiety of the formula wherein R is an unsubstituted or inertly substituted alkyl group having 1 to 6 carbon atoms, or salts thereof;
such that at least one of A, B, C, and D is (ii) and at least one is (iii).
2. The compound of Claim 1 wherein n is 0 or 1 and one of A, B, C, or D is (iii) and the remaining substituents are (ii).
3. The compound of Claim 1 wherein R is unsubstituted alkyl having 1 to 6 carbon atoms.
4. The compound of Claim 1 wherein n is 0.
5. The compound of Claim 2, 3 or 4 wherein (ii) is present in the form of a salt of the acid.
6. A process for inhibiting scale formation in an aqueous solution containing alkaline earth metal ions which compri-ses adding to said aqueous solution a threshold amount of a compound having the formula wherein (a) n is 0 to 15;
(b) A, B, C, and D are each independently selected from (i) hydrogen;
(ii) methylenephosphonic acid and salts thereof;
(iii) 2-hydroxy-3(trialkylammonium halide) propyl moieties wherein each alkyl moiety has from 1 to 5 carbon atoms; and (iv) a moiety of the formula wherein R is an unsubstituted or inertly sub-stituted alkyl group having 1 to 6 carbon atoms, and salts thereof;
such that at least one of A, B, C, and D is (ii) and at least one is (iii).
(b) A, B, C, and D are each independently selected from (i) hydrogen;
(ii) methylenephosphonic acid and salts thereof;
(iii) 2-hydroxy-3(trialkylammonium halide) propyl moieties wherein each alkyl moiety has from 1 to 5 carbon atoms; and (iv) a moiety of the formula wherein R is an unsubstituted or inertly sub-stituted alkyl group having 1 to 6 carbon atoms, and salts thereof;
such that at least one of A, B, C, and D is (ii) and at least one is (iii).
7. The process of Claim 6 wherein in the compound n is 0 or 1 and one of A, B, C, or D is (iii) and the remaining substi-tuents are (ii).
8. The process of Claim 6 wherein R is unsubstituted alkyl having 1 to 6 carbon atoms.
9. The process of Claim 5 wherein in the compound n is 0.
10. The process of Claim 7, 8 or 9 wherein (ii) is pre-sent in the form of a salt of the acid.
11. The process of Claim 7, 8 or 9 wherein (ii) is pre-sent in the form of a salt of the acid and the salt is a sodium salt.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/489,442 US4459241A (en) | 1983-04-28 | 1983-04-28 | Compounds containing quaternary ammonium and methylenephosphonic acid groups |
EP84107192A EP0165333B1 (en) | 1983-04-28 | 1984-06-22 | New compounds containing quaternary ammonium and methylenephosphonic acid groups |
Publications (1)
Publication Number | Publication Date |
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CA1229092A true CA1229092A (en) | 1987-11-10 |
Family
ID=26091888
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA000456808A Expired CA1229092A (en) | 1983-04-28 | 1984-06-18 | Compounds containing quaternary ammonium and methylenephosphonic acid groups |
Country Status (6)
Country | Link |
---|---|
US (1) | US4459241A (en) |
EP (1) | EP0165333B1 (en) |
JP (2) | JPS6118793A (en) |
AU (1) | AU572854B2 (en) |
CA (1) | CA1229092A (en) |
DE (1) | DE3476664D1 (en) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
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GB8308003D0 (en) * | 1983-03-23 | 1983-04-27 | Albright & Wilson | Phosphonates |
US4459241A (en) * | 1983-04-28 | 1984-07-10 | The Dow Chemical Company | Compounds containing quaternary ammonium and methylenephosphonic acid groups |
US4640818A (en) * | 1984-08-17 | 1987-02-03 | The Dow Chemical Company | Corrosion inhibition of metals in water systems using aminophosphonic acid derivatives in combination with manganese |
US4956107A (en) * | 1987-11-30 | 1990-09-11 | Exxon Chemical Patents Inc. | Amide dispersant additives derived from amino-amines |
US4857217A (en) * | 1987-11-30 | 1989-08-15 | Exxon Chemical Patents Inc. | Dispersant additives derived from amido-amines |
US5034018A (en) * | 1987-11-30 | 1991-07-23 | Exxon Chemical Patents Inc. | Fuel additives derived from amido-amines (PT-731) |
US4963275A (en) * | 1986-10-07 | 1990-10-16 | Exxon Chemical Patents Inc. | Dispersant additives derived from lactone modified amido-amine adducts |
US5043084A (en) * | 1987-07-24 | 1991-08-27 | Exxon Chemical Patents, Inc. | Novel polymer substituted amino phenol mannich base amido-amine dispersant additives (PT-742) |
US5124056A (en) * | 1987-07-24 | 1992-06-23 | Exxon Chemical Patents Inc. | Polymer substituted amido-amine Mannich Base lubricant dispersant additives |
US4931189A (en) * | 1988-11-02 | 1990-06-05 | Petrolite Corporation | Methods for inhibition of scale in high brine environments |
US5112496A (en) * | 1988-11-02 | 1992-05-12 | Petrolite Corporation | Methods for inhibition of scale in high brine environments |
US5252238A (en) * | 1989-05-30 | 1993-10-12 | Exxon Chemical Patents Inc. | Multifunctional viscosity index improver derived from amido-amine exhibiting improved low temperature viscometric properties |
US5230834A (en) * | 1989-05-30 | 1993-07-27 | Exxon Chemical Patents Inc. | Viscosity stable multifunctional viscosity index modifier additives derived from amido amines |
US5229020A (en) * | 1989-05-30 | 1993-07-20 | Exxon Chemical Patents Inc. | Branched amido-amine dispersant additives |
US5053151A (en) * | 1989-05-30 | 1991-10-01 | Exxon Chemical Patents Inc. | Multifunctional viscosity index improver derived from amido-amine exhibiting improved low temperature viscometric properties |
US4994195A (en) * | 1989-06-21 | 1991-02-19 | Edmondson James G | Inhibitor treatment program for chlorine dioxide corrosion |
US5213698A (en) * | 1990-07-03 | 1993-05-25 | Exxon Chemical Patents Inc. | Amido-amine ashless dispersants |
US5320829A (en) * | 1991-12-10 | 1994-06-14 | The Dow Chemical Company | Oral compositions for inhibiting plaque formation |
US5318772A (en) * | 1991-12-10 | 1994-06-07 | The Dow Chemical Company | Oral compositions for inhibiting calculus formation |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2599807A (en) * | 1950-06-01 | 1952-06-10 | Frederick C Bersworth | Alkylene polyamine methylene phosphonic acids |
US2609390A (en) * | 1950-06-01 | 1952-09-02 | Frederick C Bersworth | Phosphonic alkylene polyamino acids and method of producing same |
CH336065A (en) * | 1954-03-05 | 1959-02-15 | Ciba Geigy | Process for the preparation of new nitrogen and phosphorus containing compounds |
NL242785A (en) * | 1958-09-06 | 1900-01-01 | ||
US3336221A (en) * | 1964-11-05 | 1967-08-15 | Calgon Corp | Method of inhibiting precipitation and scale formation |
US3331773A (en) * | 1966-07-22 | 1967-07-18 | Grace W R & Co | Process for inhibiting precipitation in water |
US3434969A (en) * | 1967-08-11 | 1969-03-25 | Calgon Corp | Scale inhibiting |
US3859211A (en) * | 1968-10-17 | 1975-01-07 | Petrolite Corp | Water clarification with nitrogen-heterocyclic phosphonic acids |
US3674804A (en) * | 1968-10-17 | 1972-07-04 | Petrolite Corp | Imidazoline phosphonic acids |
US3954761A (en) * | 1968-10-17 | 1976-05-04 | Petrolite Corporation | Piperazine phosphonic acids |
US3720498A (en) * | 1968-10-17 | 1973-03-13 | Petrolite Corp | Inhibiting corrosion with nitrogenheterocyclic phosphonic acids |
US4012440A (en) * | 1970-11-18 | 1977-03-15 | Petrolite Corporation | Methylene phosphonates of oxyalkylated polyalkylene polyamines and uses therefor |
US4051110A (en) * | 1971-07-06 | 1977-09-27 | Petrolite Corporation | Methylene phosphonates of polymerized polyalkylenepolyamines |
US3743603A (en) * | 1971-08-26 | 1973-07-03 | Petrolite Corp | Inhibiting scale with nitrogen-heterocyclic phosphonic acids |
US3867286A (en) * | 1972-03-24 | 1975-02-18 | Petrolite Corp | Use of polyquaternary ammonium methylene phosphonates to chelate or inhibit formation of scale |
US3792084A (en) * | 1972-03-24 | 1974-02-12 | Petrolite Corp | Polyquaternary ammonium methylene phosphonates and uses thereof |
US4101654A (en) * | 1973-07-19 | 1978-07-18 | Petrolite Corporation | Microbiocidal process employing full quaternary nitrogen-heterocyclic phosphonates |
US3925453A (en) * | 1974-01-25 | 1975-12-09 | Monsanto Co | Quaternary aminoalkylene phosphonic acids and method of preparation |
US4234511A (en) * | 1979-07-26 | 1980-11-18 | Buckman Laboratories, Inc. | Dialkylamino-N,N-bis(phosphonoalkylene)alkylamines and use in aqueous systems as precipitation and corrosion inhibitors |
US4459241A (en) * | 1983-04-28 | 1984-07-10 | The Dow Chemical Company | Compounds containing quaternary ammonium and methylenephosphonic acid groups |
-
1983
- 1983-04-28 US US06/489,442 patent/US4459241A/en not_active Expired - Lifetime
-
1984
- 1984-06-18 CA CA000456808A patent/CA1229092A/en not_active Expired
- 1984-06-19 AU AU29499/84A patent/AU572854B2/en not_active Ceased
- 1984-06-22 EP EP84107192A patent/EP0165333B1/en not_active Expired
- 1984-06-22 DE DE8484107192T patent/DE3476664D1/en not_active Expired
- 1984-07-05 JP JP59137884A patent/JPS6118793A/en active Pending
- 1984-07-13 JP JP14456684A patent/JPS6126540A/en active Pending
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EP0165333B1 (en) | 1989-02-08 |
US4459241A (en) | 1984-07-10 |
DE3476664D1 (en) | 1989-03-16 |
AU572854B2 (en) | 1988-05-19 |
AU2949984A (en) | 1986-01-02 |
JPS6126540A (en) | 1986-02-05 |
JPS6118793A (en) | 1986-01-27 |
EP0165333A1 (en) | 1985-12-27 |
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